Method of reconstructing glyceride oils



Patented Dec. 5, 1939 UNITED STATES PATENT orrlca 2,182,332 METHOD OF RECONgIIIIIEgJCTING GLYCEBIDE George Barsky, New York, N. Y., assignor to Wecoline Products, Inc., Boonton, N. J., a corporation of New Jersey No Drawing. Application November 27, 1937, Serial No. 176,893

Claims. (01. 260-411) such as the vegetable oils, consist of a mixture v of glycerides of various fatty acids having normally from 6 to 18 carbon atoms; The properties of the different glycerides vary and generally the 1 glycerides of the lower fattyacids contained inthe mixture have lower melting points than the glycerides of the higher fatty acids in the mixture. It is often desirable to increase the melting point of the mixture contained in said oils and this in the past has been accomplished by physical means.

For example, cocoanut oil, which consists of a mixture of low and high melting constituents, has been treated by refrigeration to solidify the higher melting constituents and then subjected to a pressing operation at the low temperature whereby the liquid portions were removed. The remaining material had a higher melting point, which was highly desirable, but the entire operation was very ineificient in that the yield of the higher melting point material was low and the residual liquid could be used for purposes where its value was lessened.

The present inventionseeks to treat oils of the glyceride type having mixtures 'of low melting and higher melting point constituents, whereby the entire oil may have its melting point raised or may have other physical or chemical characteristics changed in a desiredmanner.

The present invention is based upon the dis- I covery that it is possible to displace the lower fatty acids contained in fatty oils by heating said oil with a higher fatty acid or a mixture of such higher fatty acids and then distilling off the lower fatty acids from the mixture. It has been found that the. reaction actually takes place under suitable conditions, even though it involves the displacement in a chemical combination of a stronger fatty acid by a weaker fatty acid.

v In general, the process of the present invention consists in mixing a fatty oil with a higher fatty acid having 16 or 18 carbon atoms and heating the mixture at a sufliciently high temperature. Thereby, fatty acids having from 6 to 14 carbon atoms contained in the mixed glycerides may be displaced. The lower fatty acids may then be distilled off, condensed and utilized. It is possible to "use various higher fatty acids in the process, as, for example, the saturated, unsaturated and hydroxylated fatty acids. Also, the products of the reaction may be treated in any desired manner and still further change the characteristics thereof.

The following examples will serve to illustrate the present invention: 5

Ezainple N0. 1

2720 grams of crude bleached cocoanut oil are mixed with 480 grams of distilled cottonseed fatty .acids and placed in a suitable distillingvessel. 10

The cocoanut oil had a saponification value of 258 and an iodine value of 9. The cottonseed fatty acids analyzed as follows:

FFA 102.6 Sap. number 204.7 Iodine number 101.4 Titer C 34.8

to cool and the oil and the fatty acids weighed to determine loss due to reconstruction and distil lation. Weight recoveries as high as 98.5 have thus been possible by proper condensation of the light fractions of fatty acids liberated during the reconstruction of the oil.

'A very light fraction having an FFA (free fatty acid number) well over 170.0 was found in the cold receiver of the distillation system. The average FFA of the fatty acids collected, however, lies between 1370-1430 with a correspondingly high saponification number. That some neutral oil distills or is sprayed over is apparent from the correspondingly higher saponification number of the distillate. For instance, the saponification number of the distilled fatty acids should not be 45 over 286.0 if they were pure fatty acids, but a saponification number of 298.0 to 3040 on the distillate could only mean one thing-the presence of neutral oils.

The oil obtained after the reconstruction usu- 50 ally had an FFA of about 0.35-0.60, depending upon the length of reconstruction, vacuum and steam used.

The reconstructed oils were then cooled and subjected to hydrogenation with a nickel catalyst a reflux condenser attached thereto.

was. heated. under a vacuum equal to-20-35mm.

until. the iodine. value. had dropped to. 1;. The

mixture. was then. filtered, washed with. caustic: alkali. at about 15(l."-'F'.v It was then-washed with water-until:free of-alkali; filtered, bleached with bleachingearth anddecolorizing carbon and value of 22Z3;'and after the completion of the 9 treatment. had an iodine value of 0.8. The saponification number of the oil had been reduced to: 245,, the. setting point was 31.4 0., and the.

meltingipoint. 91 F. v

Ewamplc'No. 2 I Inorder'to'reconstruct butter a mixture is pro- I vided'l containing'approximately 75%, of creamery butter. which has previously been melted, washed several timeswith water and filtered with about 25% of. distilled palm oil fatty acids. .1880 grams of this mixture. was. introduced into a still with The mass of mercury'at a temperature ranging up to about 260 C; over a period of about 2 hours. This operation resulted-in. adisplacement of the lower fatty acid'sof thebutter fat by the palm. oil fatty acids;

Thereup'on the. materialwas transferred into. a distillation system under a vacuum of about 22 (Jo-243mm. of. mercury where the distillation operatloniwas continued atv a temperature in the stock of up. to: about 2855 C. ove'ra" period of 2 or 2 hours.

This resulted. in a total recovery of reconstructedbutter fat and free fatty acids of about I862i grams, thev small amount of loss being mechanical.

. The'following. table indicates the changes which occurred in' the. various substances involved:

Sap. Iodine FFA value value Butter fat 0. 4 227. 4 35. 6 Palm oil fatty acids 104. 4 210. 2 49. 1 Mixture of 75% butter fat, 25% fatty acids. 26. 4 223.5 38. 2 Fatty acids obtained'from distillation 122. 8 250. 28. 5 Esterifled'reconstructed oil 3. 2 212. 5 40. 6

EmampZe NO. 3 h The process of the. present invention operates equally well withhydroxylated fatty acids. There was first provided a mixture containing, approximately 25% of castor: oil fatty acids and'75% of cocoanut-oil..and'2180' grams of said mixture was introduced. into a still provided with a reflux cond'ensen. Themixture'was heated under a vacuum equal? toabout. 60 mm. of mercury, the temperatureirr the stock' being up to 275 C; for ap proximateIyZF/ toB-hours; The reaction where.- by the. lower fatty acids were displaced was, for all practical purposes, complete after this period of? treatment.

- Thereafter, the-contents of the still were transiv ferred toa steam distillation equipment and held under a vacuum of approximately 12 [30.15 mm. of

mercury for a period of' 2 /2 hours while maintaining a temperature in the stock gradually rising toa maximum of about'300" 0.. As a result of this operation, the lower fatty. acids were distilled andv the. cocoanut oil Wasreconstructed. A total yield of. 2093grams'was obtained, the slight amount of loss being accounted for becausev of the. tendency of materials to adhere to the walls of the distillation vessels.

Thefollowing table indicates the changes which occurredin the various substancesinvolved:

Example N0. 4

Fully saturated higher fatty acids also operate in accordance with the present invention. For example, a mixture was made of about 15% stearic acid'with 85% cocoanut oil, and the treatment was continuedas set forth above. After the completion of the operation, the stearic acid had practically completely displaced the lower fatty acids in the cocoanut oil, which were recovered by'a distillation operation in' the usual manner.

By following the conditions, namely, the amount and character of the higher fatty acids used in combination therewith, various properties in the final products will be obtained. The products of the present invention are particu larly applicable for foodpurposes and they are useful in shortening, margerine oils, confectionary making, general cooking, frying and the like, and they are also useful in cosmetics and in pharmaceutical preparations.

Although I have described the invention setting forth several specific examples of the operation thereof, the invention is not to be limited by. the examples given herein. For instance, I may use a single fatty acid in the reconstruction of oil, or. I may use natural or artificial mixtures of fatty acids. Even the highly unsaturated fatty acids such as linoleic and clupadonic are suitable in the process. It is not necessary that the higher fatty acids have ashigh as 16 carbon atoms, but fatty acids having a lower number of carbon atoms may beused provided that thenumber is greater than that of the fatty acids to be displaced. It is not necessary that all of the lower fatty acids in the oils being reconstructed should be displaced, but I may displace allor part thereof, as desired. 7 The amount of higher fatty acid used may beless than 15% of the oil being reconstructed and may be greater than 27%.

. The conditions of" the distillation may be difier- I the invention maybe made and the invention is to be broadly construed and to be limited only by the claims appended hereto.

What I claim is:

1 A method of treating glyceride oils having in combinaton lower and higher fatty acids of from 6 to 18 carbon. atoms to alter the physical and chemical characteristics of said oils which comprises providing a mixture of said oil and a free fatty acid having at least 2 more carbon atoms than the lowest-fatty acid to be displaced but not over 18 carbon atoms. and heating said mixture to a sufiiciently high temperature wherevby a reaction takes place freeing the lower fatty acids which are replaced by said added fatty acid and removing the fatty acids so freed.

2. A method of treating glyceride oils having in combination lower and higher fatty acids of from 6 to 18 carbon atoms to alter the physical and chemical characteristics of said oils which comprises providing a mixture of said 011 and a free fatty acid having at least 2 more carbon atoms than the lowest fatty acid to be displaced but not over 18 carbon atoms, and heating said mixture to a sufficiently high temperature in a vacuum whereby a reaction takes place freeing the lower fatty acidsvwhich are replaced by said added fatty acid and removing the fatty acids so freed.

3. A method of treating glyceride oils having in combination lower and higher fatty acids of from 6 to 18 carbon atoms to alter the physical and chemical characteristics of said oils which comprises providing a mixture of said oil and an unsaturated free fatty acid having at least 2 more carbon atoms than the lowest fatty acid to be displaced but not over 18 carbon atoms, and heating said mixture to a sufficiently high temperature whereby a reaction takes place freeing the lower fatty acids which are replaced by said added fatty acid and removing the fatty acids so freed.

4. A method of treating glyceride bus having in combination lower and higher fatty acids of from 6 to 18 carbon atoms to alter'the physical and chemical characteristics of said oils, the

higher fatty acids having 16 and 18 carbon atoms and the lower fatty acids having from 6 to 14 carbon atoms,-which comprises providing a mixture of said oil and a free fatty acid having from 16 to 18 carbon atoms, and heating said mixture to a sufficiently high temperature whereby a reaction takes place freeing the lower fatty acids which are replaced by said added fatty acid and removing the fatty acids so freed.

5. A method of treating glyceride oils having in combination lower and higher fatty acids of from 6 to 18 carbon atoms to alter the physical and chemical characteristics of said oils which.

. the vaporization point of said lower fatty acids and below that of said higher fatty acids, whereby a reaction takes place freeing the lower fatty acids, which are replaced by said added fatty acid I and removing fatty acids so freed.

' GEORGE BARBKY. 

